HK1144296A - Fluorinated water soluble copolymers - Google Patents

Description

Fluorinated water-soluble copolymers

Technical Field

The present invention relates to a method of treating a substrate with a fluorinated water-soluble (meth) acrylate copolymer that can impart water repellency, oil repellency, soil resistance, soil release, stain resistance, and stain release to a substrate treated therewith.

Background

A variety of fluorinated polymer compositions are known to be useful as treating agents to provide surface effects to substrates. Surface effects include repellency, soil resistance, soil release, stain resistance and stain release, among other effects, which are particularly useful for fibrous substrates and other substrates such as hard surfaces. Many such treating agents are fluorinated polymers or copolymers.

Most commercially available fluorinated polymers useful as treating agents to impart repellency to substrates contain predominantly perfluoroalkyl chains of greater than eight carbons to provide the desired properties. Honda et al in Macromolecules (2005, 38(13)) on pages 5699 to 5705 suggest that for perfluoroalkyl chains of greater than 8 carbons, the orientation of the perfluoroalkyl chain is predominantly a parallel configuration, whereas for such fluoroalkyl chains having fewer carbons, reorientation occurs. Thus, short fluoroalkyl groups having 6 or less carbons have not traditionally been successfully commercialized for imparting surface effects to substrates due to the lack of highly ordered perfluoroalkyl chains on the outermost surface.

U.S. Pat. No. 6,833,419 discloses water-soluble or water-swellable copolymers obtained by free-radical copolymerization of acryloyldimethyltaurine and/or acryloyldimethyltaurates with one or more fluorine-containing compounds. The resulting copolymers are useful as thickeners. However, no surface effect on the substrate is disclosed in this patent publication.

There is a need for a method of treating a substrate with a water-soluble polymer composition that can impart surface effects including water repellency, oil repellency, soil resistance, soil release, stain resistance and stain release, and other effects, while using fluorinated monomers that contain perfluoroalkyl groups having eight carbons or less. The present invention provides such methods.

Summary of The Invention

The present invention includes a method of providing water repellency, oil repellency, soil resistance, soil release, stain resistance, and stain release to a substrate comprising contacting the substrate with a composition comprising a copolymer having repeating units of formula 1 in any sequence:

formula 1

Wherein

R_fIs a linear or branched perfluoroalkyl group having from about 2 to about 8 carbon atoms, optionally interrupted by at least one oxygen atom, or mixtures thereof,

Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 2 to about 15 carbon atoms, -O (C)_nH_2n)-、-(CH₂CF₂)_m(CH₂)_n-、-CONR¹(C_nH_2n)-、-(C_nH_2n)OCONR¹(C_nH_2n)-、(-CONR¹CH₂)₂CH-、-SO₂N(R¹)(C_nH_2n) -, or- (C)_nH_2n)SO₂N(R¹)(C_nH_2n)-，

Each R¹Independently H or an alkyl group having from 1 to about 4 carbon atoms,

each n is independently 1 to about 15,

each m is independently from 1 to about 4,

z is hydrogen or a methyl group,

x is a positive integer,

y is zero or a positive integer,

t is a positive integer, and

m is H⁺Alkali metal cations, alkaline earth metal cations, or ammonium.

The present invention also includes substrates treated with the composition of formula 1 described above, which have water repellency, oil repellency, soil resistance, soil release, stain resistance, and stain release properties.

Detailed Description

All trademarks are indicated in capital letters.

As used herein, the term "(meth) acrylate" means an acrylate or methacrylate.

The present invention includes a method of treating a substrate with a water soluble copolymer comprising repeating units of formula 1 in any sequence:

formula 1

Wherein

R_fIs a linear or branched perfluoroalkyl group having from about 2 to about 8 carbon atoms, optionally interrupted by at least one oxygen atom, or mixtures thereof,

q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 2 to about 15 carbon atoms, -O (C)_nH_2n)-、-(CH₂CF₂)_m(CH₂)_n-、-CONR¹(C_nH_2n)-、-(C_nH_2n)OCONR¹(C_nH_2n)-、(-CONR¹CH₂)₂CH-、-SO₂N(R¹)(C_nH_2n) -, or- (C)_nH_2n)SO₂N(R¹)(C_nH_2n)-，

Each R1 is independently H or an alkyl group having from 1 to about 4 carbon atoms,

each n is independently 1 to about 15,

each m is independently from 1 to about 4,

z is hydrogen or a methyl group,

x is a positive integer,

y is zero or a positive integer,

t is a positive integer, and

m is H⁺Alkali metal cations, alkaline earth metal cations, or ammonium.

The polymer sequence comprises random, statistical, block, multiblock, gradient, or alternating repeating units, wherein the monomers can be head-to-head or tail-to-tail. The (meth) acrylate copolymer is preferably in a head-to-tail configuration.

In formula 1, x is preferably from 1 to about 10,000, more preferably from about 1 to 5000, more preferably from about 5 to about 2000, or mixtures thereof; y is preferably from 0 to about 10,000, more preferably from about 1 to 5000, more preferably from about 5 to about 2000, or mixtures thereof; and t is preferably from 1 to about 10,000, more preferably from 1 to 5000, more preferably from about 5 to about 2000, or mixtures thereof.

R_fPreferably a straight or branched chain perfluoroalkyl group having from about 2 to about 8 carbon atoms, more preferably from about 2 to about 6 carbon atoms, and more preferably from about 4 to about 6 carbon atoms, optionally interrupted by at least one oxygen atom, or mixtures thereof. R_fUsually optionally interrupted by one to five oxygen atoms. Suitably R_fExamples of (2) include C₆F₁₃-、C₄F₉-、C₃F₇-、C₄F₉CH₂CF₂-、C₃F₇OCF₂CF₂-、C₃F₇OCHFCF₂-、C₃F₇OCF(CF₃) -, and C₃F₇O-(CF(CF₃)CF₂O)_kCFCF₃) -, where k is 1 to 4.

Q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 2 to about 15 carbon atoms, -O (C)_nH_2n)-、-(CH₂CF₂)_m(CH₂)_n-、-CONR¹(C_nH_2n)-、-(C_nH_2n)OCONR¹(C_nH_2n)-、(-CONR¹CH₂)₂CH-、-SO₂N(R¹)(C_nH_2n) -, or- (C)_nH_2n)SO₂N(R¹)(C_nH_2n) -, wherein R¹Independently H or alkyl having 1 to about 4 carbon atoms, n independently is 1 to about 15, and m is 1 to about 4. Preferred examples of Q include-CH₂CH₂-、CH₂CH(OH)CH₂-、-O(C_nH_2n)-、-(CH₂CF₂)_mCH₂CH₂-、-CONHCH₂CH₂-、-CH₂CH₂O-CONHCH₂CH₂-、(-CONHCH₂)₂CH-、-SO₂N(CH₃)CH₂CH₂-, or-SO₂N(C₂H₅)CH₂CH₂-。

-[R_f-Q-O-C(O)-C(CH₃)-CH₂]_x-repeat units or- [ R [ ]_f-Q-O-C(O)-CH-CH₂]_x-the content of recurring units, or mixtures thereof, in the copolymer is from about 10% to about 95% by weight, preferably from about 30% to about 95% by weight, more preferably from about 40% to about 80% by weight. - [ CH-CH₂-C(O)-NH-C(CH₃)₂CH₂SO3M]_t-the content of recurring units in the copolymer is from about 10 to about 70% by weight, preferably from about 15 to about 60% by weight. - [ CH₂(O)CH-CH₂-O-C(O)-C(CH₃)-CH₂]_y-the content of the repeating units is from 0% to about 10% by weight, preferably from about 0.5% to about 5% by weight.

The copolymer of formula 1 can be prepared by polymerization of the fluorinated (meth) acrylic monomer with other monomers including glycidyl methacrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid and/or metal salts thereof. The fluorinated (meth) acrylate copolymer of formula 1 may be prepared in an organic solvent or emulsified in water by free radical initiated polymerization of a fluorinated (meth) acrylic monomer in a mixture with any of the other monomers described above. The fluorinated copolymers of the present invention can be prepared by stirring the above monomers in an organic solvent or water in a suitable reaction vessel equipped with a stirring device and an external heating and cooling device. A free radical initiator is added and the temperature is raised to about 20 ℃ to about 80 ℃. Examples of the polymerization initiator are 2, 2 '-azobis (2-amidinopropane) dihydrochloride or 2, 2' -azobis (isobutylamidine) dihydrochloride. Such initiators are commercially available under the trade designation "VAZO" from e.i. du Pont de Nemours and Company (Wilmington, Delaware). An example of a suitable polymerization regulator or chain transfer agent is dodecanethiol. Organic solvents suitable for preparing the copolymer of formula 1 of the present invention include tetrahydrofuran, acetone, methyl isobutyl ketone, isopropanol, ethyl acetate, and mixtures thereof. Isopropyl alcohol is preferred. To exclude oxygen, the reaction is carried out under an inert gas such as nitrogen. The polymer is optionally isolated by precipitation and optionally purified by conventional methods such as recrystallization. The solvent is removed by evaporation, or the solution is retained, for dilution and application to a substrate. The reaction product is a fluorinated (meth) acrylate copolymer of formula 1.

The resulting fluorinated (meth) acrylate copolymer of formula 1 is then applied to a substrate as is, or diluted or emulsified in water and applied to a substrate. Alternatively, the copolymer may be further dispersed or dissolved in a simple alcohol or ketone solvent suitable for use as the solvent for final application to the substrate (hereinafter referred to as the "application solvent"). Alternatively, the solvent may be removed from the polymerization product via evaporation and an emulsification or homogenization process known to those skilled in the art may be used to prepare the aqueous dispersion. Such solvent-free emulsions are preferred to minimize flammability and Volatile Organic Compounds (VOCs). The end product applied to the substrate is a dispersion (if water-based, or emulsified in water) or a solution (if a solvent other than water is used) of the fluorinated (meth) acrylate copolymer of formula 1.

(ii) formula [ R ] for preparing the copolymer of formula 1 of the present invention_f-Q-O-C(O)-C(CH₃)＝CH₂]_xOr [ R ]_f-Q-O-C(O)-CH＝CH₂]_xExamples of suitable fluorinated (meth) acrylic monomers include the following:

C₆F₁₃CH₂CH₂O-COC(CH₃)＝CH₂、

C₆F₁₃CH₂CH₂O-COCH＝CH₂、

C₆F₁₃CH₂CH(OH)CH₂O-COC(CH₃)＝CH₂、

C₆F₁₃CH₂CH(OH)CH₂O-COCH＝CH₂、

C₄F₉CH₂CH₂O-CONHCH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CH₂O-CONHCH₂CH₂O-COCH＝CH₂、

C₄F₉CH₂CF₂-CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CF₂-CH₂CH₂O-COCH＝CH₂、

C₄F₉CH₂CF₂-CH₂CH(OH)CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CF₂-CH₂CH(OH)CH₂0-COCH＝CH₂、

C₃F₇OCF(CF₃)-CONHCH₂CH₂O-COCH＝CH₂、

(C₃F₇OCF(CF₃)-CONHCH₂)₂CHO-COCH＝CH₂、

C₃F₇OCF₂CF₂-CH₂CH₂O-COC(CH₃)＝CH₂、

C₃F₇OCF₂CF₂-CH₂CH₂O-COCH＝CH₂、

C₃F₇OCF₂CF₂-CH₂CH(OH)CH₂O-COC(CH₃)＝CH₂、

C₃F₇OCF₂CF₂-CH₂CH(OH)CH₂O-COCH＝CH₂、

C₆F₁₃SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂、

C₆F₁₃SO₂N(C₂H₅)CH₂CH₂O-COC(CH₃)＝CH₂、

C₆F₁₃SO₂N(C₂H₅)CH₂CH₂O-COCH＝CH₂、

C₆F₁₃CH₂CH₂SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₆F₁₃CH₂CH₂SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂、

C₆F₁₃SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₄F₉SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₄F₉SO₂N(C₂H₅)CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉SO₂N(C₂H₅)CH₂CH₂O-COCH＝CH₂、

C₄F₉CH₂CH₂SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CH₂SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₄F₉CH₂CF₂-SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CF₂-SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₄F₉CH₂CH₂SO₂N(C₂H₅)CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CH₂SO₂N(C₂H₅)CH₂CH₂O-COCH＝CH₂、

C₄F₉CH₂CF₂SO₂N(C₂H₅)CH₂CH₂O-COC(CH₃)＝CH₂、

C₄F₉CH₂CF₂SO₂N(C₂H₅)CH₂CH₂O-COCH＝CH₂、

C₃F₇OCF(CF₃)-SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

(C₃F₇OCF(CF₃)-SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₃F₇OCF₂CF₂-SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂、

C₃F₇OCF₂CF₂-SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂、

C₃F₇OCF₂CF₂CH₂CH₂SO₂N(CH₃)CH₂CH₂O-COC(CH₃)＝CH₂and, and

C₃F₇OCF₂CF₂CH₂CH₂SO₂N(CH₃)CH₂CH₂O-COCH＝CH₂。

among the fluorinated (meth) acrylic monomers suitable for preparing the copolymers of formula 1 of the present invention are many available from e.i. du Pont DE Nemours and Company (Wilmington, DE). Wherein Q comprises a hydroxyl group such as CH₂CH(OH)CH₂The fluorinated monomers of (A) were obtained from Aurora Fine Chemicals (Graz, A-8020, Austria) or from Fluorochem USA (West Columbia, SC).

Wherein Q is- (C)_nH_2n)OCONR¹(C_nH_2n) The fluorinated urethane (meth) acrylate monomer of (a) can be prepared by the reaction of a perfluoroalkyl alcohol with a (meth) acrylate having a reactive isocyanate group and a polymerizable vinyl double bond. Preferred conditions for the reaction are temperatures of from about-10 ℃ to about 60 ℃. Suitable optional solvents include tetrahydrofuran, methyl isobutyl ketone, acetone, hexane or ethyl acetate.

Wherein Q is (CH)₂CF₂) monomers and polymers of m (CH2) n comprising vinylidene fluoride can be prepared by using acrylic acid, methacrylic acid, 2-chloroacrylic acid using the methods as described in U.S. Pat. No. 3,282,905 and European patent 1632542A 1Or 2-fluoroacrylic acid esterification of the corresponding fluorinated alcohol and fluorinated thiol. Alternatively, acrylates and methacrylates can be prepared from the corresponding nitrates according to the method disclosed in U.S. patent publication 3,890,376.

Fluorinated alcohols useful in forming fluorinated acrylates include fluorinated telomer alcohols of formula (V):

R_f-(CH₂CF₂)_q(CH₂CH₂)_r-OH (V)

wherein R is_fIs a linear or branched perfluoroalkyl group having 2 to 8 carbon atoms. These telomer alcohols can be synthesized according to scheme 1.

Scheme 1

Telomerization of vinylidene fluoride with linear or branched perfluoroalkyl iodides to give compounds having the structure R_f(CH₂CF₂)_qA compound of I wherein q is 1 or greater, and R_fIs C₂To C₆A perfluoroalkyl group. See, for example, Balague et al, "Synthesis of fluorinated tetramers," part 1, "polymerization of vinylidine fluorides with perfluorinated compounds", "J.Fluorine chem." (1995), 70(2), pages 215 to 223. The particular telomer iodides may be separated by fractional distillation. Telomer iodides are treated with ethylene via a process as described in U.S. patent No. 3,979,469 to obtain telomer ethylene iodides (VI) where r is 1 to 3 or greater. The telomer ethylene iodides (VI) are treated with oleum and hydrolyzed to give the corresponding telomer alcohols (V). Alternatively, telomer ethylene iodides (VI) may be treated with N-methylformamide, followed by ethanol/acid hydrolysis.

The corresponding thiol of the alcohol (V) can be obtained from the telomer ethylene iodide (VI) by treatment with various reagents according to the method described in "j. fluorine Chemistry" (104, 2) pages 173 to 183 (2000). One example is the reaction of telomer ethylene iodides with sodium thioacetate, followed by hydrolysis, as shown in the following scheme:

monomers containing perfluoroalkyl ether groups are prepared from the corresponding fluorinated alcohols, fluorinated thiols, or fluorinated amines containing perfluoroalkyl ether groups.

The fluoroalcohol used to prepare the composition of the invention may be obtained by a series of reactions:

the starting perfluoroalkyl ether iodides were prepared by the method described in example 8 of U.S. patent publication 5,481,028, which discloses a method for preparing compounds of formula (V) from perfluoro-n-propyl vinyl ether.

In the above second reaction, the perfluoroalkyl ether iodide (V) is reacted with an excess of ethylene at high temperature and high pressure. When the ethylene addition reaction is carried out by heating, a suitable catalyst is preferably used. The catalyst is preferably a peroxide catalyst such as benzoyl peroxide, isobutyryl peroxide, propionyl peroxide, or acetyl peroxide. More preferably, the peroxide catalyst is benzoyl peroxide. The reaction temperature is not limited, but a temperature in the range of 110 ℃ to 130 ℃ is preferred. The reaction time varies depending on the catalyst and the reaction conditions, but 24 hours is usually sufficient. The product is purified by any method that can separate the unreacted starting materials from the final product, but distillation is preferred. Using about 2.7 moles of ethylene per mole of perfluoroalkylether iodide, a temperature of 110 ℃ and autogenous pressure, a reaction time of 24 hours, and purifying the product by distillation, yields up to 80% of the theoretical yield can be obtained, which are satisfactory.

The perfluoroalkylether ethylene iodide (VI) was treated with oleum and hydrolyzed to give the corresponding alcohol (VII). Alternatively, the perfluoroalkylether ethyl iodide may be treated with N-methylformamide followed by ethanol/acid hydrolysis. Temperatures of about 130 ℃ to 160 ℃ are preferred. Higher homologues of telomer ethylene iodides (VI) (q ═ 2, 3) can be obtained with excess ethylene at elevated pressures.

Telomer ethylene iodides (VI) are treated with various reagents to obtain the corresponding thiols according to the method described in "fluorine Chemistry" (104, 2, 2000) pages 173 to 183. One example is the reaction of telomer ethylene iodides (VI) with sodium thioacetate, followed by hydrolysis.

Telomer ethylene iodides (VI) are treated with omega-mercapto-1-alkanols according to the following scheme to obtain compounds of formula (VIII):

telomer ethylene iodides (VI) are treated with omega-mercapto-1-alkylamines according to the following scheme to obtain compounds of formula (IX):

the monomers are prepared by reaction of a fluoroalkyl carboxylic acid derivative such as hexafluoropropylene oxide dimer or hexafluoroisobutylene with a monoamine or a primary amine or a primary diamine, where Q is-CONR¹(C_nH_2n) -or (-CONR)¹CH₂)₂CH-, such as compound C₃F₇OCF(CF₃)-CONHCH₂CH₂O-COCH＝CH₂Or (C)₃F₇OCF(CF₃)-CONHCH₂)₂CHO-COCH＝CH₂. The fluoroalkylation of an amine with hexafluoroisobutylene is carried out by reacting the amine with hexafluoroisobutylene at a reaction temperature and for a reaction time sufficient to provide a secondary fluoroalkylamine having hexafluoroisobutyl groups covalently bonded to the amine. The contacting may be carried out in the presence of a solvent and/or a base catalyst. Suitable solvents include alcohols, alkyl ethers, alkyl esters, hydrocarbons, halogenated hydrocarbons, nitriles, and amides. Suitable catalysts include tertiary alkylamines, alkali metal hydroxides, and alkali metal hydrides.

The monomers being obtained by reaction of fluorosulfonyl fluoride with amines, in which Q is SO₂N(R¹)(C_nH_2n) -, or- (C)_nH_2n)SO₂N(R¹)(C_nH_2n) -. In particular, the fluorosulfonyl fluoride is reacted with methylamine or ethylamine, such as NH (CH)₃)CH₂CH₂OC(O)CH＝CH₂、NH(CH₃)CH₂CH₂OC(O)C(CH₃)＝CH₂、NH(CH₂CH₃)CH₂CH₂OC(O)CH＝CH₂Or NH (CH)₂CH₃)CH₂CH₂OC(O)C(CH₃)＝CH₂。

The present invention includes a method of providing one or more of oil repellency, water repellency, soil resistance, soil release, stain resistance, and stain release to a substrate comprising contacting a fluorinated (meth) acrylate copolymer solution or dispersion of formula 1 as described above with the substrate. Suitable substrates include fibrous substrates as defined below.

The fluorinated (meth) acrylate copolymer solution or dispersion may be contacted with the substrate by any suitable method. Such methods include, but are not limited to, administration by: exhaustion, foam, elastic nipping, padding, wet rolling, skeining, capstan, liquid injection, flooding, rollers, brushes, rollers, spraying, dipping, immersion, and the like. The copolymer may also be contacted by employing a vat dye process, a continuous dye process, or a spin line application.

The fluorinated (meth) acrylate copolymer solution or dispersion may be applied to the substrate as such or in combination with other optional fabric finishes or surface treatments. Such optional additional components include treatments or finishes that can achieve additional surface effects, or additives commonly used with such treatments or finishes. Such additional components include compounds or compositions that provide surface effects such as easy-care, shrink-control, wrinkle-free, durable-setting, moisture control, softness, strength, slip-resistance, anti-static, anti-snag, anti-pilling, stain-repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, cleanability, and the like. One or more such treatments or finishes may be applied to the substrate before, after, or simultaneously with the application of the copolymer of formula 1. For example, in the case of cellulosic substrates, when treating synthetic or cotton fabrics, it is suitable to use a wetting agent such as ALKANOL 6112 from e.i. du Pont DE Nemours and Company (Wilmington, DE). When treating cotton fabrics or cotton blend fabrics, wrinkle-free resins such as PERMAFRESH EFC from Omnova Solutions (Chester, SC) may be used.

Other additives commonly used with such treatments or finishes may also optionally be present, such as surfactants, pH adjusters, cross linkers, wetting agents, wax extenders, and other additives known to those skilled in the art. Suitable surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, N-oxides, and amphoteric surfactants. Anionic surfactants such as sodium lauryl sulfate under the tradename DUPONOL WAQE or SUPRALATE WAQE from Witco corporation (Greenwich, CT) or SUPRALATE WAQE from Witco (Houston, TX) are preferred. Examples of such additives include processing aids, blowing agents, lubricants, anti-fouling agents, and the like. The composition is applied at the manufacturing site, at the retailer site, or prior to installation and use, or at the consumer site.

Optionally, blocked isocyanates to further enhance durability are added with the copolymer of formula 1 (i.e., as a blended composition). An example of a blocked isocyanate suitable for use in the present invention is HYDROPHOBOL XAN available from ciba specialty Chemicals (High Point, NJ). Other commercially available blocked isocyanates are also suitable for use herein. The desirability of adding the blocked isocyanate depends on the particular application of the copolymer. For most of the presently envisioned applications, their presence is not required to achieve satisfactory cross-linking between warp yarns or bonding to the substrate. When added as a blended isocyanate, the amount may be added in an amount up to about 20% by weight.

Non-fluorinated extender compositions are also optionally included in the compositions of the present application to potentially further increase fluorine efficiency. Examples of such optional additional extender polymer compositions include hydrocarbon copolymers of acrylates, methacrylates, or mixtures thereof. Such copolymers may also include vinylidene chloride, vinyl acetate, or mixtures thereof.

The optimum treatment for a given substrate depends on (1) the identity of the fluorinated copolymer, (2) the identity of the surface of the substrate, (3) the amount of fluorinated copolymer applied to the surface, (4) the method of applying the fluorinated copolymer to the surface, and many other factors. Certain fluorinated copolymer repellents are suitable for use on many different substrates and repel oil, water, and many other liquids. Other fluorinated copolymer repellents exhibit excellent repellency on certain substrates or require higher loading.

The present invention also includes substrates treated with the fluorinated (meth) acrylate copolymer solution or dispersion of formula 1 as described above. Suitable substrates include fibrous substrates. The fibrous substrates include fibers, yarns, fabrics, fabric blends, textiles, nonwovens, paper, leather, and carpet. These may be made from natural or synthetic fibers including cotton, cellulose, wool, silk, rayon, nylon, aramid, cellulose acetate, acrylic, jute, sisal, seaweed, coir, polyamides, polyesters, polyolefins, polyacrylonitrile, polypropylene, aramid, or copolymers thereof. By "fabric blend" is meant a fabric made from two or more fibers. Typically these blends are a combination of at least one natural fiber and at least one synthetic fiber, but may also include blends of two or more natural fibers or blends of two or more synthetic fibers. The carpet substrate may be dyed, pigmented, printed, or naturally colored. The carpet substrate may be degummed or unglued. Substrates that can be particularly advantageously treated with the process of the present invention to impart soil resistance and soil release include those made from polyamide fibers (such as nylon), cotton, and blends of polyester and cotton, especially such substrates used in tablecloths, garments, washable uniforms, and the like. Nonwoven substrates include, for example, spunlaced nonwovens such as SONTARA available from e.i. du Pont DE nerves and Company (Wilmington, DE), and spunbond-meltblown-spunbond nonwovens. The treated substrates of the present invention have one or more of excellent water repellency, oil repellency, soil resistance, soil release, stain resistance, and stain release.

The method of the present invention can be used to provide excellent water repellency, oil repellency, soil resistance, soil release, stain resistance, and stain release to the treated substrate. Surface characteristics are obtained using copolymers containing perfluoroalkyl groups having from about 2 to about 8 carbons, preferably from about 2 to about 6 carbons. The treated substrates of the present invention can be used in a variety of applications and products, such as clothing, protective apparel, carpets, upholstery, apparel, and other uses. The superior surface characteristics described above can help keep the surface clean and therefore can be used for a longer period of time.

Test method

Test method 1-wicking and stain release test of fabrics

A. Fabric treatment

The fabric used was 100% cotton available from Textile Innovators Corporation (100 Forest Street, Windsor, NC 27983). The fabrics have different colors, weights and constructions. The resulting concentrated polymer emulsion of the present invention was diluted with deionized water to obtain a bath having 3 wt% of the final copolymer emulsion to be tested in the bath to obtain about 1000ppm by weight of fluorine on the fabric after padding and drying.

In a padding application, the treatment bath is applied to the fabric, wherein the fabric is passed through a water bath containing water and the treatment compound in about 2 seconds and at a pressure of about 20psi (137.9 x 10)³Pa) between two rollers applying pressure to obtain a wet pick-up comprised between 100% and 300% by weight. The fabric was dried at a temperature of about 160 c and held at this temperature for 3 minutes.

B. Wicking test

For wicking testing, 5 drops of DI water were dropped onto cotton samples on different areas of the material. The time (in seconds) taken for complete absorption into the fabric was measured. If the drop is not absorbed within 180 seconds, the value is recorded as 180 +. Wicking time is an indication of hydrophilicity or hydrophobicity. Short wicking times indicate high hydrophilicity, while long wicking times indicate high hydrophobicity.

C. Detergency test：

The soil release test was performed according to AATCC test method 130-1995. Five drops of mineral oil or corn oil were dropped onto a piece of blotter paper in the center of each sample treated. A piece of cellophane (weighing paper) was placed over the drop point and a five pound weight was placed over the paper. After 60 seconds, the weight and cellophane were removed. Four red dots are marked around the oil dot. The samples were placed into a Kenmore washing machine using the following settings: heavy load, warm (100 ° F, 38 ℃)/cold, one rinse, ultra clean (setting 12) and normal (fast/slow). 100g of AATCC WOB detergent and 41b material, including ballast, were added to the washing machine. After washing, the samples were allowed to stand in a high-set Kenmore dryer for 45 minutes. The samples were rated according to the following soil release swatch scale.

Grade of detergency：

Grade 5	Stain equivalent to Standard stain 5
		Class 4	Stain equivalent to Standard stain 4
Class 3	Stain equivalent to Standard stain 3
		Class 2	Stain equivalent to standard stain 2
Class 1	Stain equivalent to Standard stain 1

Grade 5 represents the best stain removal effect, while grade 1 represents the worst stain removal effect.

Test method 2 Water repellency test

The water repellency of the treated substrates was determined according to AATCC standard test Method No.193-2004 and the DuPont Technical Laboratory Method (DuPont Technical Laboratory Method) as described in the TEFLON Global Specifications and Quality Control Tests (Global Specifications and Quality Control Tests) package. The test determines the resistance of the treated substrate to wetting by aqueous liquids. Drops of hydroalcoholic mixtures of different surface tensions are placed on the substrate and the degree of surface wetting is then determined visually.

The composition of the water repellency test liquid is shown in table 1.

TABLE 1

Three drops of test liquid 1 were placed on the treated substrate. After 10 seconds, the droplets were removed by vacuum aspiration. If no liquid penetration or partial absorption (appearance of a deeper wet spot on the substrate) is observed, the test is repeated with test liquid 2. The test was repeated with test liquid 3 and progressively higher test liquid numbers were used until liquid penetration (deeper wet spots on the substrate) was observed. The test result is the highest number of test liquids that do not penetrate into the substrate. Higher values indicate greater water repellency.

Test method 3 oil repellency test

The oil repellency of the treated samples was determined via the modification of AATCC standard test method No.118, conducted as follows. Samples treated with the aqueous polymer dispersion as described in test method 1 above were held at 23 ℃ + 20% relative humidity and 65 ℃ + 10% relative humidity for a minimum of 2 hours. A series of organic liquids, as specified in table 2 below, were then added dropwise to the sample. Starting with the lowest numbered test liquid (repellency grade No.1), a drop (about 5mm diameter or 0.05mL volume) of liquid is placed at each of three locations spaced at least 5mm apart. The droplets were observed for 30 seconds. If at the end of this time two of the three drops are still spherical and there is no wicking around the drop, the next-lower-numbered three drops of liquid are placed on the adjacent site and again observed for 30 seconds. The process is continued until a test liquid appears where two of the three drops fail to remain spherical to hemispherical or where wetting or wicking occurs.

The oil repellency rating is the highest numbered test liquid with two of the three drops of liquid remaining spherical to hemispherical with no wicking for 30 seconds. Generally, treated samples rated 5 or higher were considered good to excellent. In the case of fabrics such as leather, fabrics rated one or higher may be used in certain applications.

TABLE 2 oil repellency test liquids

Oil repellency rating number	Test solution
		1	NUJOL pure mineral oil
2	65/35 volume NUJOL/n-hexadecane at 21 deg.C
		3	N-hexadecane
4	N-tetradecane
		5	N-dodecane
6	N-decane
		7	N-octane
8	N-heptane

Note that: NUJOL is a trademark of Plough, Inc. mineral oil having a Saybolt viscosity of 360/390 at 38 deg.C and a specific gravity of 0.880/0.900 at 15 deg.C.

Test method 4-accelerated staining test

A drum mill (on a roller) was used to shake the artificial soil onto the carpet sample. Synthetic soil was prepared as described in AATCC test method 123-2000, part 8. Soil-coated beads were prepared as follows. Synthetic soil (3g) and 1 liter of clean nylon resin beads (SURLYN ionomer resin beads, 1/8 to 3/16 inch (0.32 to 0.48cm) in diameter) were placed into a clean empty tank. SURLYN is an ethylene/methacrylic acid copolymer available from e.i. du Pont DE Nemours and co, Wilmington, DE. The can lid was closed and sealed with duct tape and the can was rotated on a roller for 5 minutes. Removing the soil-coated beads from the jar.

Carpet samples inserted into the drum were prepared as follows. The carpet material used was of the commercial loop (LL) type, 1245 denier, 1/10 thickness (pile separation 0.1 inch or 2.5mm), 26oz/yd²(0.88kg/m²) Dyed light yellow and obtained from Invista Inc. The total size of the carpet samples used for these tests was 8X 25 inches (20.3X 63.5 cm). Simultaneously determine oneTest samples and a control sample. The carpet pile of all samples was laid in the same direction. The shorter side (with pile courses) of each carpet sample was cut longitudinally. A strong adhesive tape is placed on the back of the carpet tile to secure them together. The carpet samples were placed in a clean, empty drum mill with the pile facing toward the center of the drum. The carpet is secured in the drum mill with rigid wires. Soil coated resin beads (250cc) and 250cc of ball bearings (5/16 inch diameter, 0.79cm) were placed into a drum mill. The drum mill lid was closed and sealed with duct tape. The roller was rotated on a roller at a speed of 105rpm for 21/2 minutes. The roll is stopped and the direction of the drum mill is reversed. The roller was rotated on the roller at a speed of 105rpm for a further 21/2 minute. The carpet samples were removed and the excess soil was removed uniformly with vacuum. The soil-coated beads were discarded.

The delta E color difference of the soiled carpet was determined for the test control compared to the original unsoiled carpet. After the accelerated soiling test, color measurements were performed on each carpet. For each control and test sample, the color of the carpet was determined, the carpet was soiled, and the color of the soiled carpet was determined. δ E is the color difference between soiled and unsoiled carpets, expressed as a positive number. The color difference was measured for each item using a Minolta chromameter CR-310. Color readings were taken on five different areas of the carpet sample and the average δ E was recorded. The control carpet for each test piece had the same color and construction as the test piece. The control carpet was not treated with any fluorochemical.

The surface effect on the carpet, including soil resistance and/or stain release, was determined from the percentage of barrier soil. The percent of barrier soil after roller soiling was calculated as% cleanliness compared to untreated soiled carpet from the following calculation.

This value is used to correct for different carpet colors and constructions and enables meaningful comparisons between data sets. Higher percentages indicate more excellent soil resistance.

Material

The following materials were used in the examples unless otherwise indicated. The abbreviations specified below are used in the tables.

1) Monomer A: 1H, 1H, 2H, 2H-perfluorooctyl acrylate, available from E.I. du Pont DE Nemours and Company (Wilmington, DE).

2) A monomer B: 1H, 1H, 2H, 2H-perfluorooctyl methacrylate, available from E.I. du Pontde Nemours and Company (Wilmington, DE).

3) AMPS: 2-acrylamido-2-methyl-1-propanesulfonic acid from Sigma-Aldrich (Milwaukee, Wis.).

4) GMA: glycidyl (meth) acrylate from Sigma-Aldrich (Milwaukee, WI).

5) BRIJ 58: polyethylene glycol cetyl ether of number average molecular weight 1124, obtained from Sigma-Aldrich.

Examples

Example 1

In example 1, a copolymer was prepared as follows. In a 500mL four-necked round bottom flask equipped with a condenser, mechanical stirrer, gas inlet and gas outlet were charged 1H, 1H, 2H, 2H-perfluorooctyl methacrylate (7.0g, 0.016mole), 1H, 2H, 2H-perfluorooctyl acrylate (3.0g, 0.0072mole), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS, 2.5g, 0.012mole), glycidyl (meth) acrylate (GMA, 0.2g, 0.0014mole), dodecanethiol (0.04g), VAZO 67(1.32g) and 2-propanol (200 g). While stirring at 150rpm for one hour at 20 ℃, dry nitrogen was gently bubbled through the solution to remove any oxygen. The nitrogen sparge was replaced with a nitrogen blanket and the reaction mixture was heated at 80 ℃ for 16 hours with stirring. The nitrogen blanket was removed and the polymer solution was allowed to cool to 20 ℃. About 150g of 2-propanol was removed by cryogenic distillation. 100mL of an aqueous solution of sodium bicarbonate (0.5g) was added to the reaction mixture. The remaining 2-propanol was removed by cryogenic distillation to obtain an aqueous dispersion of fluorinated AMPS copolymer at a pH of about 8. The copolymer solution prepared from example 1 above was applied to 100% cotton fabric using test method 1. The treated fabric was tested for wicking and hydrophilic stain removal using test method 1. The results are shown in Table 4 below.

Examples 2 to 18

In examples 2 to 18, the copolymer compounds listed in table 3 were prepared using the method described in example 1 above.

TABLE 3 copolymer Compounds

Copolymer	Monomer A (% by weight)	Monomer B (% by weight)	GMA [% by weight ]	AMPS*(wt%)
					Example 1	23.6％	55.1％	1.6％	19.7％
Example 2	7.9％	70.9％	1.5％	19.7％
					Example 3	6.8％	61.3％	2.7％	29.2％
Example 4	7.7％	69.8％	3.1％	19.4％
					Example 5	20.4％	47.7％	2.7％	29.2％
Example 6	20.7％	48.3％	1.4％	29.6％
					Example 7	0％	75.8％	1.5％	22.7％
Example 8	0％	78.7％	1.6％	19.7％
					Example 9	0％	73.0％	1.5％	25.5％
Example 10	23.5％	54.9％	1.6％	19.6％
					Example 11	15.7％	62.7％	1.6％	19.6％
Example 12	11.0％	62.3％	1.6％	24.9％
					Example 13	20.7％	48.3％	1.4％	29.6％
Example 14	18.5％	43.2％	1.2％	37.0％

Copolymer	Monomer A (% by weight)	Monomer B (% by weight)	GMA [% by weight ]	AMPS*(wt%)
					Example 15	14.9％	34.6％	0.1％	49.5％
Example 16	5.0％	44.6％	1.6％	49.5％
					Example 17	14.9％	34.6％	0.0％	49.5％
Example 18	12.9％	30.2％	0.9％	56.0％

GMA being glycidyl (meth) acrylate

AMPS is 2-acrylamido-2-methyl-1-propanesulfonic acid

The copolymer solutions prepared from examples 2 to 18 above were applied to 100% cotton fabric using test method 1. The treated fabric was tested for wicking and hydrophilic stain removal using test method 1. The results are shown in Table 4 below.

TABLE 4 wicking, stain release test

5HW represent 5 laundry washing courses according to method 1.

The data in table 4 shows that the inventive examples provide excellent performance in removing oil stains from cotton fabrics while also enabling water to wick and wet the fabric.

The copolymer solutions prepared from examples 1 to 18 above were applied to carpet samples for testing for water repellency, oil repellency, soil resistance, and soil release using test methods 2, 3, and 4. The results are shown in Table 5.

TABLE 5 testing on carpet

Compounds for administration	Water repellency	Oil repellency	Delta E (relative to untreated soiled carpet)	Cleanliness as compared with untreated soiled carpet%
					Example 1	0	5	7.7	19％
Example 2	0	5	8	26％
					Example 3	0	4	9.9	24％
Example 4	0	5	5.3	17％
					Example 5	0	5	7.9	25％
Example 6	0	5	6.6	21％
					Example 8	0	4	4.5	11％
Example 10	0	5	2.6	8％
					Example 11	0	5	0.4	1％
Example 12	0	5	7.6	22％
					Example 13	0	5	8.8	25％
Example 14	0	4	7.9	23％
					Example 15	0	2	7.5	21％
Embodiment side 16	0	2	6.3	18％

Compounds for administration	Water repellency	Oil repellency	Delta E (relative to untreated soiled carpet)	Cleanliness as compared with untreated soiled carpet%
					Example 17	0	2	4.4	13％
Example 18	0	1	3.1	9％
					Untreated	0	0	0	0％

The data in table 5 show that examples of the present invention can provide excellent oil repellency and dry soil resistance as well as soil release to treated carpets.

Examples 19 to 26

In examples 19 to 26, the copolymer compounds listed in table 6 were prepared using the method described in example 1 above.

TABLE 6 copolymer Compounds

Copolymer compound	Monomer (wt%)	GMA*(wt%)	AMPS*(wt%)
				Example 19	F-(CF2CF2CH2CH2)nO-COCH＝CH2(69.0％)	1.4％	29.6％
Example 20	(C3F7OCF(CF3)CONHCH2)2CHO-COCH＝CH2(69.0％)	1.4％	29.6％
				Example 21	C3F7OCF(CF3)CONHCH2CH2O-COCH＝CH2(69.0％)	1.4％	29.6％
Example 22	C4F9CH2CF2CH2CH2O-COCH＝CH2(69.0％)	1.4％	29.6％
				Example 23	C4F9CH2CF2CH2CH2O-COC(CH3)＝CH2(69.0％)	1.4％	29.6％
Example 24	C3F7OCF2CF2CH2CH2O-COCH＝CH2(69.0％)	1.4％	29.6％
				Example 25	C3F7OCF2CF2CH2CH2O-COC(CH3)＝CH2(69.0％)	1.4％	29.6％
Example 26	C4F9CH2CH2OCONHCH2CH2O-COC(CH3)＝CH2(69.0％)	1.4％	29.6％

GMA being glycidyl (meth) acrylate

AMPS is 2-acrylamido-2-methyl-1-propanesulfonic acid

The copolymer solutions prepared from examples 19 to 26 above were applied to 100% cotton fabric using test method 1. The treated fabric was tested for wicking and hydrophilic stain removal using test method 1. The results are shown in Table 7.

TABLE 7 wicking and stain Release test

5HW represent 5 laundry washing courses according to method 1.

The data in table 7 shows that the inventive examples provide excellent performance in removing oil stains from cotton fabrics while also enabling water to wick and wet the fabric.

The copolymer solutions prepared from examples 19 to 26 above were applied to carpet samples and tested for water repellency, oil repellency, soil resistance and soil release using test methods 2, 3 and 4. The results are shown in Table 8.

TABLE 8 testing on carpet

Compounds for administration	Water repellency	Oil repellency	Delta E (relative to untreated soiled carpet)	Cleanliness as compared with untreated soiled carpet%
					Example 19	0	3	7.12	18％
Example 21	0	3	5.14	13％
					Example 22	0	3	7.82	20％
Example 23	0	4	3.75	10％

Compounds for administration	Water repellency	Oil repellency	Delta E (relative to untreated soiled carpet)	Cleanliness as compared with untreated soiled carpet%
					Example 24	0	5	6.51	17％
Example 25	0	4	2.01	5％
					Example 26	0	3	9.43	23％
Untreated	0	0	0	0％

The data in table 8 shows that examples of the present invention can provide excellent oil repellency and dry soil resistance to treated carpets.

Example 27

In example 27, the copolymer was prepared by emulsion polymerization. In a plastic beaker, 80 grams deionized water, 2.0 grams of a 20 wt% aqueous solution of BRIJ 58, 0.04 grams dodecanethiol, 0.20 grams glycidyl (meth) acrylate (GMA), 2.5 grams 2-acrylamido-2-methyl-1-propanesulfonic Acid (AMPS), and a 3 wt% aqueous solution of sodium tetraborate (all from Sigma-Aldrich, Milwaukee, WI), 5.0 grams sulfonate AA-10 (from intercrdeHoldng, Copperhill, TN), 3.0 grams 1H, 1H, 2H, 2H-aurofluorooctyl acrylate (monomer A), and 7.0 grams 1H, 1H, 2H, 2H-perfluorooctylmethacrylate (monomer B) were mixed. The reaction mixture was heated to 55 ℃ and emulsified twice in a sonicator for two minutes each time until a homogeneous milky white emulsion was obtained. The solution was added to a 250mL flask equipped with a nitrogen blanket, condenser, overhead stirrer, and temperature probe, set to nitrogen bubbling and stirred at a rate of 170 rpm. The flask was heated to 75 ℃ over 30 minutes and switched to a nitrogen blanket. 2.0 g of a 10% by weight aqueous potassium persulfate solution (from Sigma-Aldrich, Milwaukee, Wis.) was added and stirring was maintained at 75 ℃ for 1 hour. 1.0 g of a 10% by weight aqueous solution of potassium persulfate (from Sigma-Aldrich, Milwaukee, Wis.) was added and stirring was maintained at 75 ℃ for 3 hours. The solution was then cooled to room temperature and then filtered into a narrow neck bottle through a milk filter using gravity filtration to obtain an emulsion copolymer having 13.2 wt% solids. The emulsion copolymer of example 27 was applied to 100% cotton fabric using test method 1 and the wicking and stain release properties were measured. The results are shown in Table 10.

Example 28

In example 28, copolymer compounds were prepared using the same emulsion polymerization reaction procedure as described in example 27 above, except that different amounts of monomers were used in the reaction, as described in table 9:

TABLE 9 copolymer Compounds

Copolymer compound	Monomer A (% by weight)	Monomer B (% by weight)	GMA (% by weight)	AMPS (wt%)
					Example 27	23.6％	55.1％	1.6％	19.7％
Example 28	20.7％	48.3％	1.4％	29.6％

The emulsion copolymer of example 28 was applied to 100% cotton fabric using test method 1. The treated fabric was tested for wicking and hydrophilic stain removal using test method 1. The results are shown in Table 10.

TABLE 10 wicking, stain release test

5HW represent 5 laundry washing courses according to method 1.

The data in table 10 shows that examples 27 and 28 of the present invention can provide excellent wicking and stain release properties that are durable over several laundry wash cycles.

The emulsion copolymers of examples 27 to 28 were applied to carpet samples for testing for water repellency, oil repellency, soil resistance, and soil release using test methods 2, 3, and 4. The results are shown in Table 11.

TABLE 11-soil release test on carpet

Copolymer for application	Water repellency	Oil repellency	Delta E (relative to untreated soiled carpet)	Cleanliness as compared with untreated soiled carpet%
					Example 27	4	2	0.09	0％
Example 28	5	3	1.22	3％
					Untreated	0	0	0	0％

The data in table 11 show that examples 27 and 28 of the present invention can provide excellent water repellency, oil repellency, soil resistance and detergency.

Claims (10)

1. A method of providing water repellency, oil repellency, soil resistance, soil release, stain resistance and stain release to a substrate comprising contacting the substrate with a composition comprising a copolymer having repeating units of formula 1 in any sequence:

formula 1

Wherein

R_fIs optionally provided withStraight or branched perfluoroalkyl of about 2 to about 8 carbon atoms interrupted by at least one oxygen atom, or mixtures thereof,

q is alkylene having 1 to about 15 carbon atoms, hydroxyalkylene having 2 to about 15 carbon atoms, -O (C)_nH_2n)-、-(CH₂CF₂)_m(CH₂)_n-、-CONR¹(C_nH_2n)-、-(C_nH_2n)OCONR¹(C_nH_2n)-、(-CONR¹CH₂)₂CH-、-SO₂N(R¹)(C_nH_2n) -, or- (C)_nH_2n)SO₂N(R¹)(C_nH_2n)-，

Each R¹Independently H or an alkyl group having from 1 to about 4 carbon atoms,

each n is independently 1 to about 15,

each m is independently from 1 to about 4,

z is hydrogen or a methyl group,

x is a positive integer,

y is zero or a positive integer,

t is a positive integer, and

m is H⁺Alkali metal cations, alkaline earth metal cations, or ammonium.

2. The method of claim 1, wherein R_fIndependently selected from C₆F₁₃-、C₄F₉-、C₃F₇-、C₃F₇OCF₂CF₂-、C₃F₇OCF(CF₃) -, and C₃F₇O-(CF(CF₃)CF₂O)_kCFCF₃) -, where k is 1 to 4.

3. The method of claim 1, wherein Q is selected from-CH₂CH₂-、CH₂CH(OH)CH₂-、-O(C_nH_2n)-、-(CH₂CF₂)_mCH₂CH₂-、-CONHCH₂CH₂-、-CH₂CH₂O-CONHCH₂CH₂-、(-CONHCH₂)₂CH-、-SO₂N(CH₃)CH₂CH₂-, and-SO₂N(C₂H₅)CH₂CH₂-。

4. The method of claim 1, wherein- [ R [ ]_f-Q-O-C(O)-C(CH₃)-CH₂]_x-the content of repeating units in the copolymer is about 10% by weight or more.

5. The method of claim 1, wherein- [ CH-CH₂-C(O)-NH-C(CH₃)₂CH₂SO3M]_z-the content of repeating units in the copolymer is from about 10% to about 70% by weight.

6. The method of claim 1, wherein- [ CH₂(O)CH-CH₂-O-C(O)-C(CH₃)-CH₂]_y-the content of repeating units is from 0 wt% to about 10 wt%.

7. The method of claim 1, wherein the composition is contacted with the substrate as a solution or an aqueous dispersion.

8. The method of claim 1, wherein the composition is contacted with the substrate by blotting, foaming, elastic nipping, padding, kiss-rolling, skeining, capstan, liquid injection, flooding, rolling, brushing, tumbling, spraying, dipping, or submerging.

9. The method of claim 1 wherein the composition is applied in the presence of a) at least one agent that provides a surface effect selected from the group consisting of easy iron, shrinkage control, wrinkle free, durable set, moisture control, softness, strength, slip resistance, antistatic, snag resistance, pilling resistance, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, and combinations thereof, or B) at least one surfactant, antioxidant, light fastness agent, fixing agent, water, pH adjuster, crosslinking agent, wetting agent, extender, foaming agent, processing aid, lubricant, blocked isocyanate, unfluorinated extender, or combinations thereof.

10. A substrate to which has been applied a composition according to claim 1.